Method and apparatus for converting and quenching hydrocarbons



Oct. 23, 1951 Filed Oct. 24, 1949 FIG] D. J- QUIGG ETAL METHOD AND APPARATUS FOR CONVERTING AND QUENCHING HYDROCARBONS 2 SHEETS SHEET l l a M I53 45 :5 3 44 SW23: 28 26 J; "E 49 1 25 8 42 23' i I 54 1k l l l l I .11 3| i 53 FIG. 2.

INVENTORS. D.J.QUIGG C.E. ALLEMAN ATTORNEYS Oct. 23, 1951 D. J- QUIGG EI'AL METHOD AND APPARATUS FOR CONVERTING AND QUENCHING HYDROCARBONS 2 SHEETSSHEET 2 Filed Oct. 24, 1949 FIG. 6.

mmvroks. D. J.QUIGG By c. E. ALLEMAN ATTORNEYS Patented Oct. 23, 1951 USNEI TED ES O'Fl-FEIEQE 2,572,758 METHOD A D APPARATUS FOR'CONVE'RT- 'ING AND QUENCHING'HYDR'OCARB'ONS Donald Quig-g, Bar'tlesville, Okla and Ca'rl E. 'Alleman, Cactus, Tex., assignors to :Phillips :Petroleum Company, a corporation of-Delaware Application October 24, 1949, Serial No. 123,266

12. Claims.

This invention"relates to pebble heat exchangere. lfn'oneof it's morespecific aspects it relates to a fluent solid material quench for reaction products in pebble heater apparatus. -In another of its more'specific aspects it relates to a method for preventing carbon lay-down in reaction chambers of pebble heater apparatus. In another of its more specific aspects it relates to improved pebble heat exchange apparatus.

'Th'er'i'na'l conversion processes which are 'car- 'r'i'e'd out in *s'o-calle'd pebble heater apparatus utilize -a fluent mass of 'sol-id heat exchange 'ma- ?terial, which-mass is heate'd't'o a hightemperature by passing hot gas therethrough in a fir'st direct heat exchange step and is then caused 7 to contact gaseous reactant materials, furnishing'heat thereto in a second direct heat exchange. The conventional pebble heater apparatus generally comprises two chambers which inay be disposed in substantially vertical alignment. The solid heat exchange material is introduced into the upper portion (i-f the first chamber. That material forms a moving bed of solid heat ex- -change-material which flows downwardly through the cha'mb'er in direct heat exchange with hot gaseous heatei'rchan'ge'material. The solid heat exchange mate'r'ial is heated to a high tempera- =ture in the hea t exchange and is then passed to a second chamber in "which the ho-tsolid heat exchange material is caused to contact the gaseous reactant materials in a second direct heat exchange relation, furnishing heat-for the treatment-or conversion of the-gaseous materials.

Conventional p'ebble heater chambers of pebble heater apparatus'are generally formed as cylincler's in 'whicha solid hea-texchange material is collected -in the form of -a moving bed. Hot heat exchange gases'are passed upwardly through the cylindrical bed, sometimes being introduced thereinto at the periphery of the beda'n'd-at-its lower end, and are sometimes-introduced through a refractory arch which supports the moving-pebble bed. other times, he'at is supplied to the hea'tingchamber by supplying a fuel -to the lower portion of i the pebble bed within the heater chamber 'and burning thefuel on the surface of the pebbles :so as to heat the .pebbles by combustion. Further heating of the pebbles is accompli'shed by passing the resulting combustion gas upwardly through the downflowing fluent mass pebbles.

"The heated pebbles are introduced into the upper portion of a reaction chamber. Reactant materials are introduced .into the lower portion of the reaction chamber and are caused to flow 2 upwardly through the ddwnfiowing fluent hot pebble mass therein, thereby obtaining the *heat required for thermal mmersion of the reactant materials. Reaction products are removed from the upper portion of the reaction ehambe'r g'enerally at points above the top surface or the p'ebble bed. One-disadvantage'of'theuse of 'p'ebble temperatures.

heater apparatus for theconvers'ion-of hydrocarbon materials is the fact that the reactidnp'roducts tend to accumulate in the space above the pebble bed-adjacent the surface of the reaction chamber and decompose so as to l-ay down-car bon-on the reaction chambersurface. The accumul'ation of carbon on the reaction chamber surface finally reaches such proportions as to seriously interfere 'with the removal of reaction products through the effluent outletof thereaction chamber. Additional trouble is encountered when large fragments of the-accumulated carbon separate from the surface of the reaction chamber, pass downwardly through .the chamber with the fluent mass of pebbles and become lodged in the pebble outlet of the chamber, thus reducing or p'reventing the flow of pebblesthrough the pebble heater apparatus.

Pebbles of different temperatures which :are introduced into a reaction chamber .at different points inthe top of the chamber to form a contiguous .pebble bed therein do not move laterally or intermixmaterially of their own accord. Two different .itemperature areas are thus formed in vertical sections of the chamber. Gaseous materials tend to spread through the contiguous bed and :thus encounter dissimilar .heat exchange. Little success is encountered, therefore, when attempting .to quench with cool pebbles introduced into "a :reaction chamber.

Broadly speaking, this invention comprises a meansand method of reacting hydrocarbons, by which method the accumulation of carbon in'the upper .portion rof the reaction chamber is substantially-prevented. .A plurality of pebble'portions which have been heated to different temperatures within a pebble heating chamber are used as quenching media of successively .lower The pebble portions of various temperatures are passed through a 'qu-ench chamber :so as to (form contiguous pebble beds therein which have vertical interfaces therebetween and which are disposed with relation to the .reaction chamber so that the hottest pebble bedof the q-uench'chamber is-c'ontiguous with the hot pebbles of the [reaction chamber and -.for-ms a vertical interface therebetween and the successive pebble beds .laterally disposed from the 3 reaction chamber are at successively lower temperatures. Reaction products are removed from the reaction chamber and are immediately passed through the quenching media of successively lower temperature.

Solid heat exchange material which is conventionally used in pebble heater apparatus is generally called pebbles. The term pebbles as used herein denotes any solid refractory material of flowable size and form, having strength which is suitable to carry large amounts of heat from the pebble heating chamber to the reaction chamber Without rapid deterioration or substantial breaking. Pebbles conventionally used in pebble heater apparatus are substantially spherical in shape and range from about inch to about 1 inch in diameter. In a high temperature process, pebbles having a diameter of between about inch and inch are preferred. The pebbles must be formed of a refractory material which will withstand temperatures at least as high as the highest temperature attained in the pebble heating chamber. The pebbles must also be capable or withstanding temperature changes within the apparatus. Refractory materials, such as metal alloys, ceramics, or other satisfactory material, may be utilized to form such pebbles. Silicon carbide, alurnina, periclase, thoria, beryllia, stellite, zirconia, and mullite may be satisfactorily used to form such pebbles or may be used in admixture with each other or with other materials. Pebbles formed of such materials, when properly fired, serve very well in high temperatures. Some pebbles, such as mullite-alumina pebbles, withstand temperatures up to about 3500 F. Pebbles which are used may be either inert or catalytic, as used in any selected process.

An object of this invention is to provide an improved method for operation of pebble heater apparatus. Another object of the invention is to provide improved means for quenching reaction products in pebble heater apparatus. Another object of the invention is to provide means for preventing the formation of coke adjacent reaction product outlets of reaction chambersof pebble heater apparatus. Another object of the invention is to provide an improved method for removing tarry material from reaction products.

Another object of the invention is to provide an improved pebble heater apparatus. Other and further objects and advantages will be apparent to those skilled in the art upon study of the accompanying discussion and the drawings.

Understanding of this invention will be facilitated upon reference to the diagrammatic drawings in which Figure 1 is a schematic elevation, partly in section, of a pebble heater apparatus of this invention. Figure 2 is a schematic elevation, partly in section, of a preferred modification of the pebble heater apparatus of this invention. Figure 3 is a plan view of the pebble collector taken on line 33 of Figure 2. Figure 4 is a plan view of a modified pebble collector taken on line 4-4 of Figure 1. Figure 5 is a sectional view Of a conduit portion of the pebble heater apparatus of this invention showing a modified flexible connection for one of the pebble conduits. Figure 6 is an elevation in section of a modified pebble heater chamber of this invention.

Referring particularly to the device shown in Figure l of the drawings, pebble heater chamber II comprises shell I2 which is closed at its upper and lower ends by closure members I3 and I4. Pebble inlet conduit I5 and effluent outlet conduit I6 are provided in closure member I3. Wall members I! extend from the bottom of shell I2 upwardly into a chamber formed within shell I2. Heating material inlet conduit 28 opens into the lower portion of chamber I I and preferably into that portion within bottom closure member I4. The Wall members disposed farther from heating material inlet conduit 28 preferably extend to points at successively greater heights than does the wall member nearest conduit 28. Pebble outlet conduit I8 is provided in the lowest portion of bottom closure member I4 so that it opens downward from the same chamber portion in shell I2 which is connected with conduit 28. Wall members I! preferably extend from wall to wall of shell I2 as parallel cords or tangents of circles and on the same side of conduit I8 in closure member I4. Alternately, wall members I! may be in the shape of upright conduits of circular or regular-sided cross-section. Wall members I1 form open top chamber portions within the chamber formed within shell I2, the inlet to each successive chamber portion formed between the wall members being at progressively higher points within shell I2 as the chamber portion is disposed farther from outlet conduit I8. The inlets to these chamber portions, however, must not be too high to be readily accessible to a contiguous bed of pebbles within shell I2 and extending at the natural angle of repose from pebble inlet conduit I5. It is preferable, though not essential, that the horizontal cross-sectional areas of these chamber portions be nearly equal. The Wall member I! which is nearest outlet conduit I8 preferably extends above the level of the inlet to conduit I8 a distance equivalent to between /4 and the height, of the pebble bed above conduit I8 and the open top chamber portion preferably has a cross-sectional area of between and the total cross-sectional area of chamber II.

Reactor chamber I9 is disposed below chamber II and comprises shell 2|. Shell 2I is closed at its upper end by closure member 22, which closure member slopes at an angle greater than the angle of repose of the pebbles which are in troduced into that chamber. Pebbles which are supplied to the chamber tend to assume the angle of repose which may be defined as the angle, taken from the horizontal, which the top of a pebble mass will assume when poured from a central outlet. The angle of repose generally varies between 30 and 45 from the horizontal depending upon the size, shape, and surface condition of the pebbles. Quench chamber 23, which comprises shell 24, extends laterally from the upper end of shell 2|, preferably upwardly at an angle so that its upper surface is a continuation of the slope of closure member 22. Shell 24 is closed at its upper end by closure member 25. Effluent outlet conduit 26 is provided in closure member 25 of shell 24, which closure member is opposite shell 2 I. Conduit I8 is connected to closure member 22 at a point adjacent the juncture of I shell 24 and a vertical projection of shell 2I. Pebble conduits 21 extend between the bottoms of the open top chamber portions formed between wall members I! and the top side of quench chamber 23.

Pebble collector 29 is disposed below quench chamber 23 and is connected to quench chamber 23 by means of a plurality of pebble conduits 3| which extend from points disposed along the bottom of quench chamber 23 tothe upper surface of collector member 29. The structure'of collector member 29 is more fully disclosed in must. be located far enough above. pebble outlet conduit 32 to permit natural. pebble flow from conduits; 3I to conduit. 32..

Shell 2| is closed at its bottom. end. by closure member 33 and pebble. outlet conduit 34. is pro.- vided. in closure member 33 at a point adjacent the vertical projection; of shell. 2| but is disposed on the side of chamber I9 opposite.- the side ad1-. jacent pebble conduit I 8. Reactant materialinlet conduit 35 is provided in the lower portion; of shell 2I preferably in the sideof that chamber or in the side of closure member 33 adjacent pebble outlet conduit 34. Pebble outletconduit 34 is connected at its lower end to the lower end portion of elevator 36. Pebble feeder 31, whichv may be a rotatable pebble feeder, a vibratory feeder, or the like, is provided intermediate the ends of conduit 34. Conduit 32 extends from the. bottom of collector chamber 29-to the lower end portion of elevator 36 and is provided with pebble flow control means 38 which may be a. conventional star valve, a gate valve, or some other similar type flow control means. Elevator 36 is connected at its upper end portion with the upper end of pebble inlet conduit I5. Pebble conduit39 extends between a point intermediate the ends. of pebble inlet conduit I-5 or between the upper end portion of elevator 36 and the upper end of shell 24. Alternately, the buckets of elevator 33 may be divided so as. to make separate connection between conduit 32 or conduit 34 and conduit 39. Flow control means II which may be a conventional star valve, a gate valve, or the like, is provided intermediate the ends of pebble conduit 33. Conduit 42 extends to conduit I8 and conduits 27 from an inert gas supply member.

In the operation of the device shown as Fig ure 1 of the drawings, pebbles are introduced into the upper end of chamber II throughpebble inlet.

conduit I5 which is preferably centrally disposed therein. The pebbles form a flowing contiguous bed within chamber II and .fiow downwardly through that chamber. as hot combustion gases, or a fuel is introduced heating material inlet conduit 28, If a. fuel is utilized, the fuel is burned on the surface of the pebbles contained in that portion of. the chamher which opens directly into conduit I8. The-hot combustion gases, either from an external source or, when a fuel is introduced, those resulting from the combustion of the fuel on the surface of the pebbles pass upwardly through thepebblebed and are removed from the. upper portion. of chamber II through eilluent outlet conduit I6. A per-- tion of the pebble mass within. chamber I. I passes into the open upper end of each of the chamber portions. bordered by wall members IT. The chamber portion which is closest to pebble; outlet. conduit I8 preferably has its inlet disposed at the least height within the chamber I I. The peb bles which pass into that chamber portion therefore contact the hottest heat exchange material in chamber II and are. therefore at a. relatively high temperature. Pebbles which pass intoopen ends of the chamber portions which are successively disposed farther from the heating material. inletconduit28 are atsuccessively lower tempera Heating material, such.

tures for: the! reason that their contact time with the heat exchange materials isconsiderably less.

because the pebbles: are protected from the flow of the. heating materials by the innermost wall-1- member forming the successive chamber portions and for the further reason thatthe heat exchange? material-tends to have its temperature reduced a's it progresses. farther from its inlet point..-

Ihe heated pebblesare passed through pebble conduit Iainto chamber I9 and form a flowing; contiguous: pebble mass therein. Closuremember' 22- is preferably sloping so. that no free space. is: encountered between the top of the pebble bed within chamber I9 and closure member- 22; Feb bl'es from the open top chamber portions within chamber II pass by means of pebbleconduits- 21 into quench chamber 23andform contiguouspebble beds which have vertical interfaces therebe tween. Thepebble mass from the open topcham 'bcr portion nearest tobut not opening into con' duit I8 has a vertical interface with the pebbles: which are provided to chamber I9 through pebble; ronduit I8. Reactant materials are introduced into the lower portion of chamber Iii-through conduit 3'5 and flow upwardly through that chambercountercurrent to the flow of hot pebbles therein. The hot pebbles provide the necessary heat for re action of the reactant materials. Resulting'reacw tion products flow upwardly and laterally from Q chamber I9 into chamber 23 and flow transa versely through the plurality of contiguous pebble beds'of successively lower temperatures. The; quenched products are removed from the upper end portion of chamber 23 through efiluent outs let conduit 26.

Pebbles which have been-cooled in the reaction within chamber I9 are removed therefrom through pebble outlet conduit 34 and are fed'by' means of pebble feeder 3! to elevator 36 which elevates the cooled pebbles to pebble inlet con pebble bed which is contiguous-with and cooler" than the plurality of contiguous. pebble beds."

formed by pebbles from the'open top chamber portions within chamber I I'. The lowest temper ature pebbles of this system. may be employed: in; the upper end of quench. chamber 23 by using: divided buckets in the elevator 36 and supplying direct to conduit 39 only pebbles. emerging from... the bottom of chamber I9. The remaining. por-- tion of pebbles is introduced into the upper: endv portion of chamber II.

Pebbles from quench chamber 23, which-are:

heated in the quenching process, are. withdrawn.-

from that chamber through pebble conduits 3L and are. passed into pebble collector 29 from which they are removed by means of pebblecone. Those posedequi-distant from pebbleoutlet conduit32,

the flow of pebbles from each of the open top chamber portions within chamber II is substam tially uniform, depending upon the comparative;v

size of conduits 3|. Any tarry materials which.

are laid down on the surface of the pebbles with+ in the quench chamber are burned off when those:-

pebbles are passed through pebble heater cham:

ber II. The inert gas, such as steam, WhiGh".iS-.

pebble heaterchamber ll. y 1 Referring particularly to the device shown in.

vents the flow of reaction products upwardly into Figure 2 of the drawings; chamber 44. comprises shell, 45, which is closedv at its upper end by closure member 46. Pebble inlet conduit 4-1 and.

eflluentoutlet conduit 48 are provided in closure member. 46.; Closure member .49, which is prefere.

ably in the form of a hopper, forms a portion of the bottom closure of shell 45. Wall members 50 v.extend upwardly from closure .member 5|.

scribed in connection with Figure l of the draw-.

ings.v Reaction chamber 52 comprises shell 53 which is'closed at its upper and lower ends by closure members 54and 55. Quench chamber 23 extends from the side wall of shell 53 and communicates with the chamber within shell 53 through an opening in a common wall therebetween. Quench chamber 23 comprises shell 24 which is closed at its end away from chamber 52 by closure member 25 as heretofore described. Efliuentjoutlet conduit 26 is provided in the upper end portion of chamber 23. Pebble conduits 21 extend between the open top chamber portions, formed .within chamber 44 by wall members 56, to the top side of quench chamber 23. Pebble conduits -3| extend between points disposed along the length of the bottom side of quench chamber 23 and the upper portion of pebble collector 56. Bottom closure=51 of pebble collector 56 is rotatably aflixed therein. Pebble conduits 3| extend into the top of pebble collector 56 and termipositioned far enough above pebble outlet COD- f duit 58"to permit natural pebble flow from all: the conduits'3l into conduit 58 for at least one rotational position of bottom closure 51. To assure natural pebble flow the ends of conduits 3| terminate on an are which is positioned at least of the arc radius, in a vertical distance above the pebble outlet from the pebble collector. Flexible displacement member 59, which may be a flexible, bellows, extends between'pebble outlet conduit 58 and pebble conduit 6| Pebble conduit 61 extends between flexible displacement member 59 and the lower end portion of elevator 35. Flow control means 38 is provided in pebble conduit 61. Heating material inlet conduit 28 is provided in the lower portion of shell 45 and in that portion of the chamber which is closed by. bottom.

closure member 49. Reactant material inlet conduit 35 is provided in the lower portion of reactor Pebble outlet conduit '34 extends. I

chamber 52. betwen bottom' closure member 55 of chamber 52 and the lower end portion of elevator 36.

Pebble feeder 31 is provided intermediate the ends of pebble outlet conduit 34. Elevator 36 is" connected at its upper end to pebble inlet conduit 41. Pebble conduit 39 extends between a point intermediate the ends of pebble inlet con-l duit 41 and the upper end portion of quench" chamber 23.

The operation of the device shown as Figure 2 production of ethylene.

8. of th drawings is similar to that described in connectionv with the device shown in Figure l of the drawings. The operation differs in particular with respect to pebble collector 56. By rotatingzbottom closure member 51 in pebble collector 56 to a desired point, as shown in Figure 3 of the drawings, pebble outlet conduit 58 is disposed closer to a portion of pebble conduits 3| .on their are than to the remaining portion of pebble conduits 3|. Flow of pebbles from conduits 3| which are closer to conduit 58 than the other conduits 3| is facilitated thereby while the flow from conduits 3| which are farther away is retarded. In this manner, the flow of pebbles of any desirable temperature may be selectively increased while the flow of pebbles of a different tmperature may be decreased. Flexible displacement member 59 allows bottom closure 5! to be rotated through at least a portion of a revolution without moving pebble conduit 6|.

The device shown in Figure 5 of the drawings is a modification of the conduit which extends between pebble outlet conduit 58 of pebble collector 56 and the lower portion of elevator 36. Ball and socket joints 62 or other swivel-type joints are provided at each end of pebble conduit 63 and provide the flexibility required for rotating bottom closure member 5'! in pebble collector 56.

In the device shown as Figure 6 of the drawings, chamber 64, comprises shell 65 which is closed at its upper end by closure member 66. Pebble inlet conduit 61 and efiiuent outlet conduit 68 are provided in closure member 66. The bottom of 'shell 65 is closed by closure by closure member 69. Pebble outlet conduit H is provided in the bottom'of closure member 69 and heating material inlet conduit 12 is provided in closure member 69 adjacent pebble outlet conduit 1|. Pebble outlet conduit 1| extends from a chamber portion which is surrounded by the plurality of concentric wall members 13. The wall members which are closest to the sidewall of shell 65 preferably extend upwardly to a greater height within the chamber formed within shell 65 than the wall members which form the inner-con centric chambers.

21 in their lower portions. 7

The operation of the modification shown as Figure '6 of the drawings is similar to that of the pebble heating chambers H and 44. Heat- 1 ing material is introduced into the chamber formed within the inner concentric wall mem-: ber 13 and passes upwardly through chamber 64 countercurrent to the flow of pebbles through that chamber. After heating material clears the upper edge of each of the wall members, it spreads-through the pebble bed to the next wall member and flows outwardly and upwardly chambers, respectively, and effluent material is removed through the upper portion of chamber 64 through effluent outlet conduit 68.

:This invention is particularly adaptable to crackinglight hydrocarbons, such as forthe The wall members 13 form open top chamber portions which have bottom surfaces sloping toward pebble outlet conduits are removed through The invention is also to coke.

'9 used for cracking residual hydrocarbon fractions If delayed coking is employed, this coke is laid down on the cool pebbles in the quench chamber and is subsequently removed in the heating chamber. This invention is also used for carrying out high velocity, high temperature reactions such as acetylene production which requires very short residence time and a very quick quench, thus requiring a minimum of residence time between reaching the maximum reaction temperature and being quenched below dissociating temperature.

The apparatus and the method of operation which has :been disclosed :above is very flexible and may be .used .in any number 'of operations. Various modifications and other advantages will be apparent to those skilled in the art upon study of the accompanying disclosure. The :quench maybe any convenient angle with the horizontal.

If liquid products are to be condensed from the eflluent the quench will extend somewhat downward from the "reactor. It is preferred that at least two wall member be utilized although a single wall member may be utilized when stepwise quench is not desired. Any of the modifications described or shown may be substituted in either Figure 1 or Figure 2 for members shown. It is believed that such modifications are within the spirit and the scope of the disclosure.

We claim:

1. Improved pebble heater apparatus com prising in combination a first upright closed shell; a pebble inlet conduit and an efiluent outlet conduit in the upper end of said first shell; a plurality of wall members extending from the bottom of said shell to successively different heights in the chamber formed within said shell so as to form separate open top chamber portions of successively different depths therebetween within said chamber; a second upright shell below said first shell; a third shell extending laterally from the upper portion of said second shell; a first pebble conduit extending from the bottom of the open top chamber portion which is bordered by the wall member of least height Within said first shell, to the upper end portion of said second shell; second pebble conduits extending from the bottom portion of each additional said open top chamber portions bordered by said wall members downwardly to said third shell, said second pebble conduits being spaced apart along the length of said third shell so that a second conduit extending from the chamber portion contained between the wall members having the least height and next to the least height, is connected to said third shell at the end portion attached to said second shell and each successive second conduit along said third shell extending from the bottom of said open top chamber portions bordered by wall members of successively greater height; an effluent outlet in the end of said third shell and opposite said second shell; a pebble collector; a plurality of pebble conduits extending from points spaced along the bottom of said third shell to said pebble collector; a pebble outlet conduit in the bottom of said pebble collector; a heating material inlet conduit extending into the lower portion of the open top chamber portion in said first shell which is bordered by said wall member of least height; a reactant material inlet conduit in the lower portion of said second shell; a pebble outlet conduit in the bottom of said second shell; an elevator; a third pebble conduit extending between said p'ebble outlet conduit in said second shell and the lower portion of said elevator; a :rourth pebble conduit extending between said pebble outlet conduit in said pebble collector and the lower portionof said elevator; and a firth pebble conduit extending between the upper portion of said elevator and said pebble inlet conduit in said first shell.

2. The pebble heater apparatus of claim '1, wherein said wall members form open top shells of successively greater heights, from said wall nearest said first pebble conduit to said wall farthest from said first conduit.

3. The pebble heater apparatus of claim 2, wherein said open top shells formed by said wall members are laterally aligned with and are parallel to said first pebble conduit.

4. The pebble heater apparatus of claim 1, wherein said wall member nearest said first peb bl'e conduit has a height above said first pebble conduit or between one-fourth and three-fourths the height of said pebble bed above said first pebble conduit; and said open top chamber portion which opens into said first pebble conduit has a cross-sectional area of between one-third and two-thirds the total cross-sectional area of said first chamber.

5. The pebble heater apparatus of claim 1, wherein said plurality of wall members is limited to two.

6. The pebble heater apparatus of claim 1, wherein a sixth pebble conduit extends from said fifth pebble conduit to the top of said third shell, at the end opposite said second shell; and a seventh pebble conduit extending between the bottom of said third shell, at the end opposite said second shell, and said pebble collector.

7. The pebble heater apparatus of claim 1, wherein said wall members form concentric shells of successively greater heights from the central portion toward the periphery of said first shell, said first pebble conduit and said heating material inlet conduit extending to said open top chamber enclosed by the innermost said wall member; and the bottom of each annular open top chamber formed by said concentric walls is sloped to the inlet points of said second conduits therein.

8. The pebble heater apparatus of claim 1, wherein said wall members are upright parallel plane members which extend from wall to wall of said first shell on the same side of said first pebble conduit; and said wall members are of successively greater height from the one nearest said first pebble conduit to the one farthest from said pebble conduit.

9. The pebble heater apparatus of claim 1, wherein a sixth pebble conduit extends from said fifth pebble conduit to the top of said third shell, at the end opposite said second shell; a seventh pebble conduit extends between the bottom of said third shell, at the end opposite said second shell, and said pebble collector; and said plurality of pebble conduits and said seventh pebble conduit extend from said third shell into said pebble collector and terminate therein on an are located a vertical distance equal to at least five-eighths the radius of said arc above said pebble outlet in the bottom of said pebble collector and having an axis common with the axis of the pebble outlet in the bottom of said pebble collector.

10. The pebble heater apparatus of claim 1, wherein said first pebble conduit extends into said second shell at a point adjacent the up- .11 right projection of the wall of said second shell and adjacent said third shell; and said pebble outlet conduit in the bottom of said second shell is offset therein adjacent the wall of said second shell; on the side opposite said first pebble conduit.

11. A method for reacting fluids in the presence of hot particulate solids and quenching resulting reaction products, which comprises in com bination the steps of passing particulate solid material into a heating zone; passing a hot gas upwardly through said heating zone in direct heat exchange with said particulate solid material, whereby said particulate solid material is heated; removing gaseous efiluent material from the-upper portion of said heating zone;

gravitating a portion of said heated particulate solid material from the bottom of said heating zone into a reaction zone; introducing reactant fluid into the lower portion of said reaction zone and reacting said materials in the presence of said heated solids; gravitating other portions of said solid heat exchange material from selected points throughout the vertical length of 12 said heating zone and at different .tempera' tures to a quenching zone; passing resulting reaction products from said reaction zone trans- ,versely and successively through said other solid heat exchange material portions of said particulate solid material from the material portion at the highest temperature through the material portion at the lowest temperature; removing quench products from said quenching zone; gravitating said solid material from said reaction zone; and gravitating said solid material.

from said quenching zone.

12. The method of claim 11, wherein a portion of the solid material withdrawn from said reaction zone and said quench zone is passed to said quench zone as the coolest particulate solid material therein; and the balance of said solid material from said reaction zone and said quench zone is passed to the upper portion of said heating zone.

DONALD J. QUIGG. CARL E. ALLEMAN.

No references cited. 

11. A METHOD FOR REACTING FLUIDS IN THE PRESENCE OF HOT PARTICULATE SOLIDS AND QUENCHING RESULTING REACTION PRODUCTS, WHICH COMPRISEES IN COMBINATION THE STEPS OF PASSING PARTICULATE SOLID MATERIAL INTO A HEATING ZONE; PASSING A HOT GAS UPWARDLY THROUGH SAID HEATING ZONE IN DIRECT HEAT EXCHANGE WITH SAID PARTICULATE SOLID MATERIAL, WHEREBY SAID PARTICULATE SOLID MATERIAL IS HEATED; REMOVING GASEOUS EFFLUENT MATERIAL FROM THE UPPER PORTION OF SAID HEATING ZONE; GRAVITATING A PORTION OF SAID HEATED PARTICULATE SOLID MATERIAL FROM THE BOTTOM OF SAID HEATING ZONE INTO A REACTION ZONE; INTRODUCING REACTANT FLUID INTO THE LOWER PORTION OF SAID REACTION ZONE AND REACTING SAID MATERIALS IN THE PRESSENCE OF SAID HEATED SOLIDS;F GRAVITATING OTHER PORTIONS OF SAID SOLID HEAT EXCHANGE MATERIAL FROM SELECTED POINTS THROUGHOUT THE VERTICAL LENGTH OF SAID HEATING ZONE AND AT DIFFERENT TEMPERATURES TO A QUENCHING ZONE, PASSING RESULTING REACTION PRODUCTS FORM SAID REACTION ZONE TRANSVERSELY AND SUCCESSIVELY THROUGH SAID OTHER SOLID HEAT EXCHANGE MATERIAL PORTIONS OF SAID PARTICULATE SOLID MATERIAL FROM THE MATERIAL PORTION AT THE HIGHEST TEMPERATURE THROUGH THE MATERIAL PORTION AT THE LOWEST TEMPERATURE; REMOVING QUENCH PRODUCTS FROM SAID QUENCHING ZONE; GRAVITATING SAID SOLID MATERIAL FROM SAID REACTION ZONE; AND GRAVITATING SAID SOLID MATERIAL FROM SAID QUENCHING ZONE. 